pyscf-vscf

pyscf-vscf is a public-alpha package for PySCF-backed construction and reduced-dimensional variational analysis of vibrational potential-energy and dipole-moment surfaces.

The package now contains an actual state-specific VSCF solver for n-mode Hamiltonians with one-mode terms and explicit two-mode coupling corrections. It also provides 1D/2D sinc-DVR solvers, overlap-based 2D state assignment, harmonic and scan workflows, exact constrained normal-coordinate relaxation, and provenance-checked PES/DMS caches.

VCI is not implemented. The present VSCF is reduced-dimensional and uses rectilinear uniform DVR coordinates with diagonal one-mode kinetic operators. The package does not claim full-dimensional or general curvilinear VSCF/VCI.

Install

Install the current alpha from PyPI:

pip install "pyscf-vscf==0.1.0a4"

Install the PySCF-backed workflows as well:

pip install "pyscf-vscf[pyscf]==0.1.0a4"

The source project uses uv for development:

uv sync --extra dev

Install the optional electronic-structure backend for PySCF calculations:

uv sync --extra dev --extra pyscf

Pure numerical modules and the VSCF solver do not import PySCF.

Runnable VSCF Example

The wheel includes a deterministic, PySCF-free coupled two-mode example:

uv run python -m pyscf_vscf.examples.vscf_two_mode

The main API is:

from pyscf_vscf import NModePotential, VSCFSettings, vscf_spectrum

NModePotential represents

H = sum_i [T_i + V_i(q_i)] + sum_{i<j} V_ij(q_i, q_j)

where each V_ij is a coupling correction rather than a complete two-mode potential. Coordinates supplied to NModePotential must be in Angstrom.

The current VSCF implementation consumes a one-mode/two-mode PES through the Python API. nmode_model_from_pair_surfaces assembles that representation from overlapping complete pair surfaces, rejects inconsistent shared one-mode cuts, and removes independent pair-energy offsets. PySCF does not yet generate an arbitrary molecular n-mode PES or DMS automatically. VSCF transition intensities and a VSCF command-line workflow are also not implemented.

Command Line

The geometry commands below are source-checkout examples; geom/ is repository validation material and is not installed into the wheel:

pyscf-vscf --help
pyscf-vscf --version
pyscf-vscf --mmol geom/HDO.mmol --task harmonic --dispersion none
pyscf-vscf --mmol geom/H2O.mmol --task 1d --bond 0-1 --npts 41

PySCF-backed work requires the pyscf extra. The legacy pyscf_pme_pipeline.py remains in the source repository for historical compatibility, but release support and API guarantees apply to the package code under src/pyscf_vscf.

XYZ and MMOL files do not reliably preserve molecular charge and spin. Supply --charge and --spin whenever a non-neutral or open-shell geometry is reused.

Scientific Conventions

• Transition dipoles are reported in Debye, never arbitrary units.
• Integrated cross sections are integral sigma(omega) d omega in m^2/s.
• Axis-projected values are for polarized light; vector-norm values use the isotropic 1/3 orientation average.
• 2D state labels use phase-canonical wavefunction overlaps and expose unique labels, mixed-state signatures, participation ratios, dominant-manifold weights, and leading signed components.
• Schema-v2 caches fingerprint geometry, isotope masses, charge/spin, every electronic-structure setting, scan coordinates, runtime versions, and array checksums. Legacy caches fail closed in production loaders.

See the intensity conventions and validation guide.

Validation

uv run ruff check src tests scripts/validate_archived_grids.py \
  scripts/generate_nh3_three_mode.py scripts/expand_nh3_three_mode.py \
  scripts/validate_nh3_three_mode.py
uv run ruff format --check src tests scripts/validate_archived_grids.py \
  scripts/generate_nh3_three_mode.py scripts/expand_nh3_three_mode.py \
  scripts/validate_nh3_three_mode.py
uv run pytest -q
uv run --extra pyscf pytest -m pyscf -q
uv run python scripts/validate_archived_grids.py \
  --nmax 12 --output validation_data/convergence_report.json
uv run python scripts/validate_nh3_three_mode.py

The archived-grid analysis performs no electronic-structure recomputation. It reports state-matched spreads across grid density and coordinate-window variants for H2O, HDO, and D2O. It also compares the two assigned stretch fundamentals of each isotopologue against independent ORCA harmonic IR intensities. The six calculated intensities reproduce the independent scale and isotope/mode trend within 35.4% relative error. This is a computational cross-check, not an experimental or rovibrational validation.

On the same archived molecular surfaces and a matched separable kinetic model, state-specific VSCF is also compared with exact 2D DVR for both fundamentals and their combination state. This is a molecular solver benchmark, not an independent validation of the underlying PES or omitted kinetic couplings.

The separate NH3 archive exercises three local N-H coordinates and all three pair surfaces. State-specific VSCF is compared with exact 3D DVR on the identical 1MR/2MR Hamiltonian across a documented window-convergence sequence. The fundamental, binary-combination, and triple-combination manifolds pass the 25 cm^-1 centroid-spread criterion; the first-overtone manifold is retained as nonconverged. Across the final three variants, the maximum VSCF/exact centroid error is 4.43 cm^-1. Reanalysis uses only the checked-in caches and does not require PySCF.

Release Status

The current version is 0.1.0a4. API changes remain possible during alpha. The repository includes an MIT license, citation metadata, changelog, CI, GitHub release automation, an opt-in trusted-publishing workflow, and a release checklist. Original validation data are separately licensed under CC BY 4.0; see DATA_LICENSE.md in the source repository.